CN107492634B - binder-free Li3V2(PO4)3/C composite lithium ion battery anode and preparation method thereof - Google Patents

binder-free Li3V2(PO4)3/C composite lithium ion battery anode and preparation method thereof Download PDF

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CN107492634B
CN107492634B CN201710556602.9A CN201710556602A CN107492634B CN 107492634 B CN107492634 B CN 107492634B CN 201710556602 A CN201710556602 A CN 201710556602A CN 107492634 B CN107492634 B CN 107492634B
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CN107492634A (en
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倪世兵
唐俊
康桃
杨学林
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China Three Gorges University CTGU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a method for preparing a carbon composite lithium vanadium phosphate binder-free anode by using an intermediate liquid phase method, which comprises the specific steps of weighing a lithium source and a vanadium source in a small beaker, adding deionized water, stirring for 20min until the lithium source and the vanadium source are completely dissolved, transferring the mixture into a hydrothermal liner, adding the deionized water to 80% of the volume of the liner, and carrying out hydrothermal treatment in a blast oven at 100-180 ℃ for 12-48 h. Weighing a phosphorus source and an organic carbon source in a beaker, adding deionized water, stirring for 20min until the phosphorus source and the organic carbon source are completely dissolved, then slowly dropwise adding the naturally-cooled intermediate phase liquid into the beaker in which the phosphorus source and the organic carbon source are dissolved, stirring for 20min until the solution becomes orange yellow, and heating and concentrating to a certain volume. And then soaking the carbon substrate in the liquid-phase precursor for 1-4 hours, and drying in a blast oven at 60 ℃ for 24-36 hours. And pre-burning the dried carbon matrix at 350 ℃ for 2-6 h in a nitrogen atmosphere, calcining at 650-850 ℃ for 6-12 h, and naturally cooling to obtain the binder-free Li3V2(PO4)3/C electrode which is used as the anode of the lithium ion battery and shows better electrochemical performance.

Description

Binder-free Li3V2(PO4)3/C composite lithium ion battery anode and preparation method thereof
Technical Field
The invention relates to a high-performance adhesive-free lithium ion battery anode, in particular to a preparation method of a Li3V2(PO4)3/C composite material electrode, and belongs to the field of electrochemical power sources.
Technical Field
Lithium ion batteries are currently the main power source for portable electronic devices because of their high energy density, high safety, low self-discharge, long life, and no memory. Meanwhile, the power supply is also considered as an ideal power supply for future electric vehicles, field communication and large energy storage power stations. The research and development of high-performance lithium ion batteries are always important subjects of battery enterprises and research institutes at home and abroad, and the key for determining the success or failure of the high-performance lithium ion batteries lies in the research and application of high-performance lithium ion electrodes.
The conventional electrode preparation process mixes an active material, a conductive agent, and a binder, and coats the mixture on a metal current collector. The introduction of the conductive agent and the bonding agent can increase the weight of the battery and reduce the energy density of the battery. And the active material is indirectly contacted with the conductive current collector through a conductive agent, so that the electron transmission process in the electrode is directly influenced, and the rate performance of the battery is limited. The electrode material is directly grown on the conductive current collector in an in-situ growth mode, so that the electrical contact between the active material and the current collector can be obviously enhanced, and the capacity loss caused by a conductive agent and a binder can be effectively reduced, thereby obviously improving the performance of the battery. Currently, there are many reports on in-situ growth of lithium ion battery negative electrode materials on a conductive current collector, but there are few reports on direct growth of positive electrode materials. The existing anode material is mainly a multi-component system and comprises lithium cobaltate, lithium manganate, lithium iron phosphate, ternary materials and the like, most of the preparation methods are solid-phase reaction methods, and the reaction process is complex. On one hand, the multielement material is difficult to keep good contact with the conductive matrix, and in-situ growth is realized; on the other hand, it is difficult to achieve uniform reaction among a plurality of reaction raw materials, thereby obtaining a uniform positive electrode material.
Li3V2(PO4)3 is a novel anode material, has a high charging and discharging platform and reversible capacity (the theoretical capacity is 133 mAh g-1 when the voltage is 3-4.3V), has good thermal stability and cost advantage, and has strong practical value. The invention discloses an intermediate liquid phase method for preparing a Li3V2(PO4)3/C binder-free positive electrode. On one hand, the intermediate liquid phase has higher viscosity, which is beneficial to uniform adsorption on the carbon matrix; on the other hand, the intermediate liquid phase can realize uniform mixing of reactants, and Li3V2(PO4)3 particles with uniform size are obtained; meanwhile, the intermediate liquid phase is beneficial to introducing a carbon source, the intermediate liquid phase crystallization can induce organic carbon source molecules to be uniformly adsorbed on the surface of the intermediate liquid phase in the drying process and to be carbonized in situ in the subsequent solid phase reaction, and the uniform compounding of Li3V2(PO4)3 and C on a microscopic scale is realized. Finally, the prepared binderless Li3V2(PO4)3/C electrode as a lithium ion battery positive electrode shows excellent electrochemical performance.
Disclosure of Invention
The invention relates to a preparation method of a lithium ion battery anode, wherein the anode is a composite structure formed by in-situ growth of Li3V2(PO4)3/C on a carbon substrate. The active substance is a Li3V2(PO4)3/C composite material, consisting of particles with an average size of about 100 nm. The preparation method comprises the following steps: dissolving a certain amount of lithium source, vanadium source and hexamethylenetetramine in deionized water, and stirring for 30min until the lithium source, the vanadium source and the hexamethylenetetramine are fully dissolved; and transferring the obtained mixed solution into a hydrothermal liner, adding deionized water to 80% of the volume of the liner, carrying out hydrothermal treatment in a blast oven at 100-180 ℃ for 12-48 h, and naturally cooling to obtain an intermediate phase liquid. Weighing a certain amount of carbon source and phosphorus source, dissolving in deionized water, stirring for 20min until the carbon source and the phosphorus source are fully dissolved, slowly dropwise adding the cooled intermediate phase liquid, and stirring for 30min after the dropwise adding is finished until the color is orange yellow. Then the liquid is dried in a blast oven at 60 ℃ to different volume concentrations; and soaking the carbon substrate in the liquid obtained after concentration for 1-4 hours, and drying in a blast oven at 60 ℃ for 24-36 hours. And pre-burning the dried carbon matrix at 350 ℃ for 2-6 h in a nitrogen atmosphere, calcining at 650-850 ℃ for 6-12 h, and naturally cooling to obtain the binder-free Li3V2(PO4)3/C electrode.
The molar ratio of the lithium, the vanadium, the phosphorus and the hexamethylene tetramine is 3: 2: 3: 2 to 10. The carbon source accounts for 0-10% of the total mass. The lithium source is lithium carbonate, lithium hydroxide, lithium acetate or lithium oxalate, the vanadium source is vanadium pentoxide or ammonium metavanadate, the phosphorus source is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate, and the carbon source is citric acid, glucose, sucrose or ascorbic acid.
The preparation method, the structure and the performance of the Li3V2(PO4)3/C electrode without the adhesive have the following remarkable characteristics:
(1) The electrode synthesis process is simple, easy to operate and good in repeatability;
(2) Li3V2(PO4)3/C is uniformly compounded with the carbon matrix and is in good contact with the carbon matrix;
(3) The prepared Li3V2(PO4)3/C is in particle morphology and has an average size of about 200 nm;
(4) the Li3V2(PO4)3/C binderless electrode prepared by the invention can be directly used as the anode of a lithium ion battery and shows better cycle performance and higher specific capacity.
Drawings
FIG. 1 SEM image of a sample prepared in example 1.
fig. 2 graph (a) of the first three charge and discharge curves and graph (b) of the cycle performance of the sample prepared in example 1.
FIG. 3 is a graph of the cycle performance of the samples prepared in example 2.
FIG. 4 cycle performance plot of the samples prepared in example 3.
Detailed Description
Example 1
weighing 3mmol of lithium carbonate, 2mmol of vanadium pentoxide and 5mmol of hexamethylenetetramine, dissolving in a small beaker filled with 20mL of deionized water, and stirring for 30min until the lithium carbonate, the vanadium pentoxide and the hexamethylenetetramine are fully dissolved; and transferring the obtained mixed solution into a hydrothermal liner, adding deionized water to 80% of the volume of the liner, performing hydrothermal treatment in a blast oven at 120 ℃ for 24 hours, and naturally cooling to obtain intermediate phase liquid. Weighing 0.05g of citric acid and 6mmol of ammonium dihydrogen phosphate, dissolving in a beaker filled with 20mL of deionized water, stirring for 20min until the citric acid and the ammonium dihydrogen phosphate are fully dissolved, then slowly dropwise adding the cooled intermediate phase liquid into the beaker, and stirring for 30min after the dropwise adding is finished until the color is orange yellow. And then, drying the liquid in the beaker in a blast oven at 60 ℃ until the volume is concentrated to half of the original volume, soaking the graphene foam in the liquid obtained after concentration for 2 hours, and drying in the blast oven at 60 ℃ for 30 hours. And pre-burning the dried graphene foam for 4h at 350 ℃ in a nitrogen atmosphere, calcining for 8h at 750 ℃, and naturally cooling to obtain the binder-free Li3V2(PO4)3/C electrode. SEM characterization was performed on the sample, and from FIG. 1, it can be seen that Li3V2(PO4)3/C was uniformly grown on the graphene surface and consisted of particles with a size of about 100 nm. The above electrodes were cut into a size of 1X 1 cm, and vacuum-dried at 120 ℃ for 12 hours. A metal lithium sheet is used as a counter electrode, a Celgard membrane is used as a diaphragm, a solution of EC + DEC (volume ratio of 1:1) dissolved with LiPF6 (1mol/L) is used as an electrolyte, and the CR2025 type battery is assembled in a glove box protected by argon. And standing for 8 hours after the battery is assembled, and then performing constant-current charging and discharging tests by using a CT2001A battery test system, wherein the test voltage is 3-4.3V. Fig. 2 shows that the first charge and discharge capacities of the Li3V2(PO4)3/C binderless electrode prepared in example 1 were 134.6 and 109.3 mAh/g, respectively, and the charge and discharge capacities after 100 cycles were 109.8 and 109 mAh/g, respectively, showing better electrochemical properties.
example 2
Weighing 3mmol of lithium oxalate, 2mmol of vanadium pentoxide and 5mmol of hexamethylenetetramine, dissolving in a small beaker filled with 20mL of deionized water, and stirring for 30min until the lithium oxalate, the vanadium pentoxide and the hexamethylenetetramine are fully dissolved; and transferring the obtained mixed solution into a hydrothermal liner, adding deionized water to 80% of the volume of the liner, performing hydrothermal treatment in a blast oven at 120 ℃ for 24 hours, and naturally cooling to obtain intermediate phase liquid. 0.05g of glucose and 6mmol of ammonium dihydrogen phosphate are weighed and dissolved in a beaker filled with 20mL of deionized water, stirred for 20min until the glucose and the ammonium dihydrogen phosphate are fully dissolved, then the cooled intermediate phase liquid is slowly dripped into the beaker, and stirred for 30min after the dripping is finished until the color is orange yellow. And then, drying the liquid in the beaker in a blast oven at 60 ℃ until the volume is concentrated to half of the original volume, soaking the carbon cloth in the liquid obtained after concentration for 2 hours, and drying in the blast oven at 60 ℃ for 30 hours. And pre-burning the dried carbon cloth at 350 ℃ for 4h in a nitrogen atmosphere, calcining at 750 ℃ for 8h, and naturally cooling to obtain the binder-free Li3V2(PO4)3/C electrode. The cell was assembled in the manner of example 1. FIG. 3 shows that the first charge and discharge capacities of the Li3V2(PO4)3/C binderless electrode prepared in example 2 were 133.3 and 121.3 mAh/g, respectively, and the charge and discharge capacities after 90 cycles were 119 and 119.1 mAh/g, respectively, showing better electrochemical properties.
Example 3
Weighing 3mmol of lithium hydroxide, 2mmol of ammonium metavanadate and 5mmol of hexamethylenetetramine, dissolving in a small beaker filled with 20mL of deionized water, and stirring for 30min until the lithium hydroxide, the ammonium metavanadate and the hexamethylenetetramine are fully dissolved; and transferring the obtained mixed solution into a hydrothermal liner, adding deionized water to 80% of the volume of the liner, performing hydrothermal treatment in a blast oven at 120 ℃ for 24 hours, and naturally cooling to obtain intermediate phase liquid. Weighing 0.03g of citric acid and 3mmol of ammonium dihydrogen phosphate, dissolving in a beaker filled with 20mL of deionized water, stirring for 20min until the citric acid and the ammonium dihydrogen phosphate are fully dissolved, then slowly dropwise adding the cooled intermediate phase liquid into the beaker, and stirring for 30min after the dropwise adding is finished until the color is orange yellow. And then, drying the liquid in the beaker in a blast oven at 60 ℃ until the volume is concentrated to half of the original volume, soaking the carbon paper in the liquid obtained after concentration for 2 hours, and drying in the blast oven at 60 ℃ for 30 hours. And pre-burning the dried carbon paper at 350 ℃ for 4h in a nitrogen atmosphere, calcining at 750 ℃ for 8h, and naturally cooling to obtain the binder-free Li3V2(PO4)3/C electrode. The cell was assembled in the manner of example 1. Fig. 3 shows that the Li3V2(PO4)3/C binderless electrode prepared in example 3 has first charge and discharge capacities of 142.1 and 111.7 mAh/g, respectively, and has charge and discharge capacities of 93.5 and 92.1 mAh/g, respectively, after 90 cycles, showing better electrochemical properties.

Claims (1)

1. The Li3V2(PO4)3/C composite electrode of the binderless lithium ion battery is characterized in that the binderless lithium ion battery is a composite electrode, the particle component is Li3V2(PO4)3/C which is uniformly grown on a carbon matrix, and the preparation process of the binderless electrode is as follows:
Weighing 3mmol of lithium carbonate, 2mmol of vanadium pentoxide and 5mmol of hexamethylenetetramine, dissolving in a small beaker filled with 20mL of deionized water, and stirring for 30min until the lithium carbonate, the vanadium pentoxide and the hexamethylenetetramine are fully dissolved; transferring the obtained mixed solution into a hydrothermal liner, adding deionized water to 80% of the volume of the liner, performing hydrothermal treatment in a blast oven at 120 ℃ for 24 hours, and naturally cooling to obtain a mesophase liquid; weighing 0.05g of citric acid and 6mmol of ammonium dihydrogen phosphate, dissolving in a beaker filled with 20mL of deionized water, stirring for 20min until the citric acid and the ammonium dihydrogen phosphate are fully dissolved, then slowly dropwise adding the cooled intermediate phase liquid into the beaker, and stirring for 30min after the dropwise adding is finished until the color is orange yellow; then, drying the liquid in the beaker in a blast oven at 60 ℃ until the volume is concentrated to half of the original volume, soaking the graphene foam in the liquid obtained after concentration for 2 hours, and drying in the blast oven at 60 ℃ for 30 hours; and pre-burning the dried graphene foam for 4h at 350 ℃ in a nitrogen atmosphere, calcining for 8h at 750 ℃, and naturally cooling to obtain the binder-free Li3V2(PO4)3/C electrode.
CN201710556602.9A 2017-07-10 2017-07-10 binder-free Li3V2(PO4)3/C composite lithium ion battery anode and preparation method thereof Active CN107492634B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102386412A (en) * 2011-11-11 2012-03-21 中南大学 Lithium ion battery anode Li3V2(PO4)3/C composite material and preparation method thereof
CN104779393A (en) * 2015-04-15 2015-07-15 河北民族师范学院 Method for preparing lithium-vanadium-phosphate lithium ion battery positive material by means of liquid phase reduction
CN104868119A (en) * 2015-04-16 2015-08-26 三峡大学 Binder-free Li3VO4/C lithium ion battery cathode material and preparation method thereof
CN106654218A (en) * 2017-01-11 2017-05-10 湖南文理学院 Lithium ion battery positive electrode material lithium vanadium phosphate/carbon, preparation method thereof and lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102386412A (en) * 2011-11-11 2012-03-21 中南大学 Lithium ion battery anode Li3V2(PO4)3/C composite material and preparation method thereof
CN104779393A (en) * 2015-04-15 2015-07-15 河北民族师范学院 Method for preparing lithium-vanadium-phosphate lithium ion battery positive material by means of liquid phase reduction
CN104868119A (en) * 2015-04-16 2015-08-26 三峡大学 Binder-free Li3VO4/C lithium ion battery cathode material and preparation method thereof
CN106654218A (en) * 2017-01-11 2017-05-10 湖南文理学院 Lithium ion battery positive electrode material lithium vanadium phosphate/carbon, preparation method thereof and lithium ion battery

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